Alkenyl ether compound, polymer compound, composition using them, and image formation method and apparatus

ABSTRACT

A polymer compound is provided which is suitable to improve the dispersibility of coloring materials or solids in an ink or toner composition and which has a repeating unit represented by the general formula (2): (2) wherein X′ represents a polyalkenyl group; each A represents independently a linear or branched alkylene group of 1 to 15 carbon atoms which may be substituted; m represents an integer of 0 to 30; B represents a single bond or an alkylene group which may be substituted; each D represents independently an aromatic ring in which at least one hydrogen atom attached to the ring is displaced by a fluorine atom; n represents an integer of 1 to 10; and R represents a hydrogen atom, an alkyl group which may be substituted, or an aromatic ring which may be substituted.

TECHNICAL FIELD

The present invention relates to a novel alkenyl ether compound usefulas various types of functional material, a polymer compound, acomposition using them, and an image formation method and apparatususing the above composition. Particularly preferably, it relates to anink composition and a toner composition in which these compounds areused with a solvent or dispersion medium and a coloring material, and animage formation method and apparatus using these compositions.

BACKGROUND ART

Aqueous dispersion materials containing a functional substance haveconventionally been known widely as functional materials, such asagricultural chemicals such as herbicides or insecticides,pharmaceuticals such as antitumor agents, antiallergic agents orantiphlogistics, and coloring materials such as ink or toner containinga coloring agent. In particular, coloring materials are dissolved ordispersed, so as to prepare an ink composition or toner composition.“Journal of Polymer Science Part A, Polymer Chemistry” Vol. 27, pp. 3303to 3314, 1989 discloses a preferred use of various polymer materials, inwhich vinyl polymers such as styryl, acryl or methacryl polymers areused. With regard to a coloring material composition comprising asolvent or water as a base material, an attempt has generally been madethat a polymer material preferably comprising an ionic functional groupis used, so as to improve dispersibility of coloring materials such aspigments. In addition, using such toner compositions or inkcompositions, digital printing techniques have been highly developed inrecent years. Electrophotography and ink-jet technique arerepresentative examples of such digital printing techniques, and inthese years, the presence of such techniques have been increasinglyenhanced as image formation techniques applied both in office and home.

Among others, the ink-jet technique is a direct recording methodcharacterized in that it is compact in scale, resulting in low powerconsumption. In addition, image quality is being rapidly improved byminiaturization of nozzles or the like. Examples of such ink-jettechniques include a method comprising heating an ink supplied from anink tank with a heater in a nozzle so as to evaporate the ink and forman ink bubble, and then ejecting the ink bubble to form an image oh arecording medium. Another example is a method of vibrating piezoelements to elect an ink from a nozzle. Since an aqueous dye solutionhas been commonly used as ink used in these methods, there have beensome cases where smearing has been occurred, or a phenomenon calledfeathering has been appeared in the fiber direction of paper at arecording area on a recording medium, when different colors wereoverlaid. U.S. Pat. No. 5,085,698 describes that the use of pigmentdispersion ink has been studied to improve the above problems. However,it is still desired that many other improvements have been made for suchink.

DISCLOSURE OF THE INVENTION

The present invention has been accomplished under the above-describedcircumstances and provides a polymer compound and a block polymerpreferably used to improve the dispersibility of functional substances.

Moreover, the present invention provides a functional composition usingthe above polymer or block polymer, and in particular, a recordingmaterial such as an ink composition or toner composition, and an imageformation method, a liquid application method and an apparatus using theabove compositions.

The present inventors have conducted intensive studies regarding theabove prior art techniques and problems, thereby completing the presentinvention described below.

The present invention provides an alkenyl ether compound comprising atleast one of an aromatic carboxylic acid having a fluorine atom and anaromatic carboxylic acid ester having a fluorine atom, which ispreferably represented by the general formula (1):XO(AO)_(m)B(D)_(n)COOR  (1)wherein X represents an alkenyl group; each A represents independently alinear or branched alkylene group of 1 to 15 carbon atoms which may besubstituted; m represents an integer of 0 to 30; B represents a singlebond or an alkylene group which may be substituted; each D representsindependently an aromatic ring in which at least one hydrogen atomattached to the ring is replaced by a fluorine atom; n represents aninteger of 1 to 10; and R represents a hydrogen atom, an alkyl groupwhich may be substituted, or an aromatic ring which may be substituted.

Moreover, the present invention provides a polymer compound comprising apolyalkenyl ether repeating unit comprising at least one selected from acarboxylic acid, a carboxylic acid ester and a carboxylic acid salt,each having a fluorine atom in a side chain thereof, which preferablyhas a repeating unit represented by the general formula (2) or (3):

wherein X′ represents a polyalkenyl group; each A representsindependently a linear or branched alkylene group of 1 to 15 carbonatoms which may be substituted; m represents an integer of 0 to 30; Brepresents a single bond or an alkylene group which may be substituted;each D represents independently an aromatic ring in which at least onehydrogen atom attached to the ring is displaced by a fluorine atom; nrepresents an integer of 1 to 10; and R represents a hydrogen atom, analkyl group which may be substituted, or an aromatic ring which may besubstituted; or

wherein X′ represents a polyalkenyl group; each A representsindependently a linear or branched alkylene group of 1 to 15 carbonatoms which may be substituted; m represents an integer of 0 to 30; Brepresents a single bond or an alkylene group which may be substituted;each D represents independently an aromatic ring in which at least onehydrogen atom attached to the ring is displaced by a fluorine atom; nrepresents an integer of 1 to 10; and M represents a monovalent orpolyvalent metal cation.

Furthermore, the present invention provides a block polymer whichcomprises a polyalkenyl ether repeating unit comprising an aromaticstructure having a fluorine atom in a side chain thereof in at least oneblock segment, wherein the aromatic structure is at least one selectedfrom a carboxylic acid, a carboxylic acid ester and a carboxylic acidsalt.

Still further, the present invention provides a composition whichcomprises a solvent or dispersion medium, a functional substance, andthe polymer compound or block polymer in accordance with the presentinvention.

Still further, the present invention provides an image recording methodthat comprises the steps of preparing the composition in accordance withthe present invention and recording the composition on a medium.

Still further, the present invention provides an image recordingapparatus that comprises a recording means for recording the compositionin accordance with the present invention on a medium.

By polymerizing the novel polymeric compound of the present invention,it is possible to provide a polymer compound that is preferably used toprepare an ink or toner composition in which coloring materials orsolids are well dispersed.

Further, by mixing the polymer compound of the invention with a solventor a dispersing medium and a coloring material, it is possible toprovide a composition such as an ink or toner composition, and arecording material.

Moreover, it is possible to provide a variety of image forming methodsand apparatuses that employ recording materials such as ink or tonercompositions using the polymer of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram showing the structure of an ink-jet recordingapparatus; and

FIG. 2 is a view showing NMR of the polymeric compound of Example 1 ofthe present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below.

The present invention is an alkenyl ether compound that comprises atleast one of an aromatic carboxylic acid having a fluorine atom and anaromatic carboxylic acid ester having a fluorine atom, which is apolymeric compound preferably represented by the general formula, (1):XO(AO)_(m)B(D)_(n)COOR  (1)wherein X represents an alkenyl group; each A represents independently alinear or branched alkylene group of 1 to 15 carbon atoms which may besubstituted; m represents an integer of 0 to 30; B represents a singlebond or an alkylene group which may be substituted; each D representsindependently an aromatic ring in which at least one hydrogen atomattached to the ring is replaced by a fluorine atom; n represents aninteger of 1 to 10; and R represents a hydrogen atom, an alkyl groupwhich may be substituted, or an aromatic ring which may be substituted.

Preferred examples of the alkenyl group include ethynyl, propenyl,butenyl, pentenyl and hexenyl.

It is preferably a compound represented by the following general formula(5):CH₂═CHO(AO)_(m)B(D)_(n)COOR  (5)

In the above general formula (5), A represents a linear or branchedalkylene group of 1 to 15 carbon atoms, preferably 2 to 10 carbon atoms,which may be substituted. Examples of the substituent for the alkylenegroup include methyl, ethyl, propyl and phenyl.

In the above general formula (5), m represents an integer of 0 to 30,preferably 1 to 10. When m is 2 or more, the respective A's may be thesame or different from each other.

In the above general formula (5), B represents a single bond or analkylene group which may be substituted. Examples of such an alkylenegroup include methylene, ethylene, propylene, butylenes, pentylene,hexylene, heptylene and octylene.

In the above general formula (5), D represents an aromatic ring in whichat least one hydrogen atom attached to the ring is displaced by afluorine atom. Examples of such an aromatic ring include phenyl,pyridylene, pyrimidyl, naphthyl, anthranyl, phenanthranyl, thiophenyland furanyl. The types of substitution include monofluoro substitution,difluoro substitution, trifluoro substitution, tetrafluoro substitution,and substitution with more numbers of fluorine atoms such as 5, 6, 7 or8 fluorine atoms. However, it is preferable that the aromatic ring issubstituted with at least two fluorine atoms.

In the above general formula (5), n represents an integer of 1 to 10,preferably of 1 to 5. When n is 2 or more, the respective D's may be thesame or different from each other.

In the above general formula (5), R represents a hydrogen atom, an alkylgroup which may be substituted, or an aromatic ring which may besubstituted. As the alkyl group, alkyl groups of 1 to 10 carbon atomsare preferable. Examples of the aromatic ring include a phenyl group, apyridyl group and a biphenyl group. Examples of the substituent includean alkyl group and an alkoxy group.

The fluorine-substituted aromatic carboxylic acids represented by thegeneral formula (1) have acidities different from those of the aliphaticcarboxylic acids and are therefore extremely useful in their feasibilityof providing various functional polymer materials with differentacidities as polymer compounds having the vinyl ether repeating units.Also from the viewpoint of increasing the acidity, it is preferable thatthe aromatic ring is substituted with at least two fluorine atoms.Moreover, in order to control the property of each block segment relatedto fluorophilicity or fluorophobicity, it is preferable that thearomatic ring is substituted with as many fluorine atoms as possible.

Specific examples of the polymeric compound represented by the generalformula (1) include the following compounds:CH₂═CHOCH₂CH₂OPh(4F)COOC₂H₅CH₂═CHOCH₂CH₂OPh(4F)COOHCH₂═CHOCH₂CH₂OPh(4F)COOCH₃CH₂═CHOCH₂CH₂Ph(3F)COOC₂H₅CH₂═CHOCH₂CH₂OPh(F)PhCOOC₂H₅CH₂═CHOCH₂CH₂ONp(2F)COOC₂H₅CH₂═CHOCH₂CH₂OPh(F)COOC₂H₅CH₂═CHOCH₂CH₂CH₂OPh(3F)COOCH₃CH₂═CHOCH₂CH(CH₃)OPh(3F)COOC₂H₅CH₂═CHOCH₂CH(C₂H₅)OPh(3F)COOC₂H₅CH₂═CHOCH₂CH (C₃H₇)OPh(3F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₂Ph(3F)COOC₃H₇CH₂═CHO(CH₂CH₂O)₂Ph(2F)COOCH₃CH₂═CHO(CH₂CH₂O)₂Ph(2F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₃Ph(4F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₂Np(F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₃Np(4F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₃Np(5F)COOHCH₂═CHOCH₂CH₂O(CH₂)₂Ph(3F)COOCH₃CH₂═CHOCH₂CH₂O(CH₂)₃Ph(3F)COOCH₃CH₂═CHOCH₂CH₂O(CH₂)₄PhPh(3F)COOCH₃CH₂═CHOCH₂CH₂O(CH₂)₅Np(3F)COOCH₃CH₂═CHO(CH₂CH₂O)₆Ph(3F)COOCH₃CH₂═CHO(CH₂CH₂O)₇PhPh(3F)COOCH₃CH₂═CHOCH₂CH₂O(CH₂CH₂CH₂O)₂Ph(3F)COOCH₃CH₂═CHOCH₂CH₂OPyPh(2F)COOCH₃CH₂═CHOCH₂CH₂OPyPh(2F)COOC₂H₅CH₂═CHOCH₂CH₂O(CH₂)₂₀Ph(2F)COOCH₃CH₂═CHO(CH₂CH₂O)₂(CH₂)₂Ph(2F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₃(CH₂)₃Ph(2F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₁₀Ph(2F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₂₀Ph(2F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₂(CH₂)₆OPh(2F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₅(CH₂)₇OPh(3F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₆(CH₂)₈OPh(3F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₁₀(CH₂)₁₀OPh(3F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₁₅(CH₂)₁₅OPh(3F)COOC₂H₅CH₂═CHO(CH₂CH₂O)₂(CH₂)₂₀OPh(3F)COOC₂H₅CH₂═CHOCH₂CH₂CH₂CH₂CH₂CH₂CH₂O(CH₂)₂OPh(3F)COOC₂H₅CH₂═CHOCH₂CH₂CH₂CH₂O(CH₂)₃OPh(3F)COOC₂H₅CH₂═CHOCH₂CH₂CH₂CH₂O(CH₂)₄OPh(3F)COOC₂H₅CH₂═CHOCH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂O(CH₂)₅OPh(3F)COOC₂H₅CH₂═CHOCH₂CH₂CH₂CH₂CH₂CH₂O(CH₂)₆OPh(3F)COOC₂H₅CH₂═CHOCH(CH₃)CH₂O(CH₂)₇OPh(3F)COOC₂H₅CH₂═CHOCH(CH₃)CH₂O(CH₂)₈OPh(3F)COOC₂H₅CH₂═CHOCH₂CH(CH₃)O(CH₂)₁₀OPh(3F)COOC₂H₅CH₂═CHOCH(C₂H₅)CH₂O(CH₂)₁₅OPh(4F)COOC₂H₅CH₂═CHOCH₂CH(CH₃)O(CH₂)₂₀OPh(2F)COOC₂H₅CH₂═CHOCH₂CH₂O(CH₂)₂OPh(3F)COOPhHCH₂═CHOCH₂CH₂O(CH₂)₃OPh(3F)COOCH₂PhHCH₂═CHOCH₂CH₂O(CH₂)₄OPh(4F)COOPyrHCH₂═CHOCH₂CH₂CH₂CH₂O(CH₂)₅OPyr(3F)COOPhHCH₂═CHOCH₂CH₂O(CH₂)₆OPh(3F)COOPh(OCH₃)CH₂═CHO(CH₂CH₂O)₂(CH₂)₇OPh(F)COOPh(OCH₃)CH₂═CHOCH₂CH₂O(CH₂)₈OPh(4F)COOPh(OCH₃)CH₂═CHOCH₂CH₂O(CH₂)₁₀OPh(3F)COOPh(OCH₃)CH₂═CHOCH₂CH₂O(CH₂)₁₅OPh(2F)COOPh(OCH₃)CH₂═CHOCH₂CH₂O(CH₂)₂₀OPh(3F)COOPh(OCH₃)

In the above examples, Ph represents 1,4-phenylene or 1,3-phenylene, Pyrepresents 2,5-pyrimidylene, and Pyr represents 2,5-pyridylene. Nprepresents 2,6-naphthylene, 1,4-naphthylene or 1,5-naphthylene. Theexpression Ph (F) represents 2- or 3-monofluoro substitution. Theexpression Ph (2F) represents 2,3-, 2,6-, 2,5- or 3,5-difluorosubstitution. The expression Ph(3F) represents 2,3,5- or 2,3,6-trifluorosubstitution. The expression Ph(4F) represents 2,3,5,6-tetrafluorosubstitution. In the case of other aromatic ring structures also, thearabic numeral in parentheses represents the number of fluorine atomsfor substitution and indicates that the substitution is effected at anypositions.

As an example of the synthesizing method of the polymeric compoundrepresented by the general formula (1), there may be included anetherification method shown by the following reaction formula (1):

wherein X represents a halogen atom.

Moreover, the present invention is a polymer compound comprising apolyalkenyl ether repeating unit comprising at least one selected from acarboxylic acid, a carboxylic acid ester and a carboxylic acid salt,each having a fluorine atom in a side chain thereof, which preferablyhas a repeating unit represented by the general formula (2):

wherein X′ represents a polyalkenyl group; each A representsindependently a linear or branched alkylene group of 1 to 15 carbonatoms which may be substituted; m represents an integer of 0 to 30; Brepresents a single bond or an alkylene group which may be substituted;each D represents independently an aromatic ring in which at least onehydrogen atom attached to the ring is displaced by a fluorine atom; nrepresents an integer of 1 to 10; and R represents a hydrogen atom, analkyl group which may be substituted.

The repeating unit structure represented by the general formula (2) ispreferably a unit structure represented by the following general formula(6):

wherein each A represents independently a linear or branched alkylenegroup of 1 to 15 carbon atoms which may be substituted; m represents aninteger of 0 to 30; B represents a single bond or an alkylene groupwhich may be substituted; each D represents independently an aromaticring in which at least one hydrogen atom attached to the ring isdisplaced by a fluorine atom; n represents an integer of 1 to 10; and Rrepresents a hydrogen atom, an alkyl group which may be substituted, oran aromatic ring structure which may be substituted.

Incidentally, it is to be noted that preferred ranges and specificexamples of A, m, B, D, n and R are the same as those described for theabove general formula (1).

The general formula (6) in accordance with the present invention ischaracterized by having the fluorine-substituted aromatic carboxylicacid derivative at a terminal thereof. The fluorine-substituted aromaticcarboxylic acids have acidities different from those of the aliphaticcarboxylic acids and are therefore extremely useful in their feasibilityof providing various functional polymer materials with differentacidities as polymer compounds having the vinyl ether repeating units.Also from the viewpoint of increasing the acidity, it is preferable thatthe aromatic ring is substituted with at least two fluorine atoms.Moreover, in order to control the property of each block segment relatedto fluorophilicity or fluorophobicity, it is preferable that thearomatic ring is substituted with as many fluorine atoms as possible.

Specific examples of the repeating unit structure represented by thegeneral formula (2) include the following unit structures:

In the above examples, Ph represents 1,4-phenylene or 1,3-phenylene, Pyrepresents 2,5-pyrimidylene, and Pyr represents 2,5-pyridylene. Nprepresents 2,6-naphthylene, 1,4-naphthylene or 1,5-naphthylene. Theexpression Ph(F) represents 2- or 3-monofluoro substitution. Theexpression Ph(2F) represents 2,3-, 2,6-, 2,5- or 3,5-difluorosubstitution. The expression Ph(3F) represents 2,3,5- or 2,3,6-trifluorosubstitution. The expression Ph(4F) represents 2,3,5,6-tetrafluorosubstitution. In the case of other aromatic ring structures also, thearabic numeral in parentheses represents the number of fluorine atomsfor substitution and indicates that the substitution is effected at anypositions.

The polymer compound having the repeating unit structure represented bythe above general formula (2) can preferably be obtained by polymerizingthe polymeric compound represented by the above general formula (1). Thepolymerization herein is mainly a cationic polymerization. Examples ofan initiator used herein include a protonic acid such as hydrochloricacid, sulfuric acid, methanesulfonic acid, trifluoroacetic acid,trifluoromethanesulfonic acid or perchloric acid, or a combination of aLewis acid such as BF₃, AlCl₃, TiCl₄, SnCl₄, FeCl₃, RAlCl₂ orR_(1.5)AlCl_(1.5) (wherein R represents alkyl) with a cation source(wherein examples of such a cation source include a protonic acid, andan adduct obtained from water, alcohol, vinyl ether and a carboxylicacid). By making such an initiator coexist with the polymeric compound(monomer) represented by the general formula (1), a polymerizationreaction will proceed to synthesize the polymer compound.

The number-average molecular weight of the polymer of the presentinvention having the repeating unit structure represented by the generalformula (2) is generally not less than 200 but no more than 10,000,000,and preferably not less than 1,000 but no more than 1,000,000. If thenumber-average molecular weight exceeds 10,000,000, it causes too muchentanglement or twisting in a polymer chain or between polymer chains,and it might become difficult for the polymer to be dispersed in asolvent. In contrast, if the number-average molecular weight is lessthan 200, the molecular weight is so small that a steric effect as apolymer might be hardly obtained. The polymer of the present inventionmay be either a homopolymer consisting of a single kind repeating unitstructure, or copolymer consisting of multiple kinds of repeating unitstructures. The repeating unit structure represented by the generalformula (2) may be contained in the polymer preferably in an amount of10 mol % or more. In addition, the content of the polyalkenyl etherrepeating unit structure may also be preferably 50 mol % or more, andmore preferably 80 mol % or more.

Moreover, the polymer of the present invention is a polymer having arepeating unit structure represented by the following general formula(3):

wherein X′ represents a polyalkenyl group; each A representsindependently a linear or branched alkylene group of 1 to 15 carbonatoms which may be substituted; m represents an integer of 0 to 30; Brepresents a single bond or an alkylene group which may be substituted;each D represents independently an aromatic ring in which at least onehydrogen atom attached to the ring is displaced by a fluorine atom; nrepresents an integer of 1 to 10; and M represents a monovalent orpolyvalent metal cation.

Preferred examples of the polyalkenyl include polyethynyl, polypropenyl,polybutenyl, polypentenyl and polyhexenyl.

The repeating unit structure represented by the general formula (3) ispreferably a unit structure represented by the following general formula(7):

wherein each A represents independently a linear or branched alkylenegroup of 1 to 15 carbon atoms which may be substituted; m represents aninteger of 0 to 30; B represents a single bond or an alkylene groupwhich may be substituted; each D represents independently an aromaticring in which at least one hydrogen atom attached to the ring isdisplaced by a fluorine atom; n represents an integer of 1 to 10; and Mrepresents a monovalent or polyvalent metal cation.

It is to be noted that preferred ranges and specific examples of A, m,B, D and n are the same as those described for the above general formula(1).

In the above general formula (7), M represents a monovalent orpolyvalent metal cation. Specific examples of M as a monovalent metalcation include sodium, potassium and lithium. Specific examples of M asa polyvalent metal cation include magnesium, calcium, nickel and iron.When M represents a polyvalent metal cation, M forms counterions for twoor more COO⁻ groups as anions.

The polymer of the present invention having the repeating unit structurerepresented by the general formula (3) can be obtained by subjecting toalkaline hydrolysis or alkaline neutralization, a terminal ester portionof a corresponding polymer having the repeating unit structurerepresented by the above general formula (2). It is also possible toobtain the above polymer of the present invention by hydrolysis with anacid followed by alkaline treatment. However, the former method ispreferable.

Specific examples of the repeating unit structure represented by thegeneral formula (3) include the following unit strictures:

In the above examples, Ph represents 1,4-phenylene or 1,3-phenylene, Pyrepresents 2,5-pyrimidylene, and Pyr represents 2,5-pyridylene. Nprepresents 2,6-naphthylene, 1,4-naphthylene or 1,5-naphthylene. Theexpression Ph(F) represents 2- or 3-monofluoro substitution. Theexpression Ph(2F) represents 2,3-, 2,6-, 2,5- or 3,5-difluorosubstitution. The expression Ph(3F) represents 2,3,5- or 2,3,6-trifluorosubstitution. The expression Ph(4F) represents 2,3,5,6-tetrafluorosubstitution. In the case of other aromatic ring structures also, thearabic numeral in parentheses represents the number of fluorine atomsfor substitution and indicates substitution is effected at anypositions.

The number-average molecular weight of the polymer of the presentinvention having the repeating unit structure represented by the generalformula (3) is generally not less than 200 but no more than 10,000,000,and preferably not less than 1,000 but no more than 1,000,000. If thenumber-average molecular weight is more than 10,000,000, it causes toomuch entanglement or twisting in a polymer chain or between, polymerchains, and it might become difficult for the polymer to be dispersed ina solvent. In contrast, if the number-average molecular weight is lessthan 200, the molecular weight is so small that a steric effect as apolymer might be hardly obtained. The polymer of the present inventionmay be either a homopolymer consisting of a single kind repeating unitstructure, or copolymer consisting of multiple kinds of repeating unitstructures. The repeating unit structure represented by the generalformula (3) may be contained in the polymer preferably in an amount of10 mol % or more. In addition, the content of the polyalkenyl etherrepeating unit structure may also be preferably 50 mol % or more, andmore preferably 80 mol % or more.

Next, the fourth aspect of the present invention is a block polymer,which comprises a polyalkenyl ether repeating unit comprising anaromatic structure having a fluorine atom in a side chain thereof in atleast one block segment. The term block polymer is used to mean acopolymer obtained by binding at least two different types of polymersegment structures by covalent bonding, and such a block polymer is alsocalled a block copolymer. Moreover, the block polymer of the presentinvention is preferably a block polymer comprising a polyalkenyl etherrepeating unit comprising at least one selected from a carboxylic acid,a carboxylic acid ester and a carboxylic acid salt, each having afluorine atom in a side chain thereof in at least one block segment.Furthermore, when the above structure is a fluorine-substituted aromaticcarboxylic acid structure, the pKa of the carboxylic acid is preferably2.5 or less. The fact that the pKa is 2.5 or less means that thecompound can sufficiently be in a dissociative state up to a pH close to3, which shows extremely stable ionicity and hydrophilicity. It is to benoted that pKa is an acid dissociation index and represents thelogarithmic value of the reciprocal of an acid dissociation constant Ka.When the concentration of a certain acid (HA) that is not dissociated ina solution is defined as [HA], and when the concentration of adissociated acid H⁺ and the concentration of its counterion are definedas [H⁺] and [A⁻], respectively, the acid dissociation constant Ka isexpressed as Ka=[H⁺][A⁻]/[HA]. Accordingly, pKa is obtained by thefollowing expression: pKa=−log[H⁺]−log([A⁻]/[HA])=pH−log([A⁻]/[HA]).Incidentally, in the present invention, pKa is obtained, while a polymeris not defined as a unit of the number of moles, but one carboxylic acidrepeating unit is defined as a unit of the number of moles.

The block polymer of the present invention is preferably a block polymerhaving in at least one block segment thereof, a repeating unit structurerepresented by the following general formula (4):

wherein X′ represents a polyalkenyl group; each A representsindependently a linear or branched alkylene group of 1 to 15 carbonatoms which may be substituted; m represents an integer of 0 to 30; Brepresents a single bond or an alkylene group which may be substituted;each D represents independently an aromatic ring in which at least onehydrogen atom attached to the ring is displaced by a fluorine atom; nrepresents an integer of 1 to 10; p represents 0 or 1; and COORrepresents a carboxylic acid ester, a carboxylic acid, or a salt of acarboxylic acid anion and a cation.

Specific examples of the repeating unit structure represented by thegeneral formula (4) include the above listed examples of the repeatingunit structures represented by the general formulas (2) and (3). Inaddition, specific examples further include those in which thecarboxylic acid moieties of the above listed structures are substitutedwith hydrogen or fluorine atoms.

The block polymer of the present invention does not only have a blocksegment containing the repeating unit structure represented by the abovegeneral formula (4), but also have a block segment containing at leastanother repeating unit structure. More specifically, a block segmentcontaining a repeating unit represented by the following general formula(8) is preferably used:

wherein:

R¹ is selected from the group consisting of a linear, branched or cyclicalkyl group of 1 to 18 carbon atoms, -Ph, -Pyr, -Ph-Ph, -Ph-Pyr,—(CH(R⁵)—CH(R⁶)—O)_(p)—R⁷ and —(CH₂)_(m)—(O)_(n)—R⁷, and hydrogenatom(s) in the aromatic ring may be replaced by linear or branched alkylgroup(s) of 1 to 4 carbon atoms, and carbon atom(s) in the aromatic ringmay be replaced by nitrogen atom(s);

p represents an integer of 1 to 18;

m represents an integer of 1 to 36;

n represents 0 or 1;

each of R⁵ and R⁶ represents independently a hydrogen atom or —CH₃;

R⁷ is selected from the group consisting of a hydrogen atom, a linear,branched or cyclic alkyl group of 1 to 18 carbon atoms, -Ph, -Pyr,-Ph-Ph, -Ph-Pyr, —CHO, —CH₂CHO, —CO—CH═CH₂, —CO—C(CH₃)═CH₂ and—CH₂COOR₈, and when R⁷ is other than a hydrogen atom, hydrogen atom(s)attached to carbon atom(s) in R⁷ may be replaced by a linear or branchedalkyl group of 1 to 4 carbon atoms, —F, —Cl or —Br, and carbon atom(s)in the aromatic ring may be replaced by nitrogen atom(s);

R⁸ represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms;

Ph represents a phenyl or phenylene group; and

Pyr represents a pyridyl group.

Specific examples of the R¹ structure represented by the general formula(8) are as follows:

In the above examples, Ph represents a phenyl or phenylene group.

Moreover, each block segment of the block polymer of the presentinvention may consist of a single kind repeating unit, or may consist ofmultiple kinds of repeating unit structures. Examples of a block segmentconsisting of multiple kinds of repeating units include a randomcopolymer and a graduation copolymer whose compositional ratio isgradually changed. Furthermore, the block polymer of the presentinvention is a block polymer having two or more block segments and mayalso be a graft polymer obtained by graft binding of the above blockpolymer to other polymers.

In the present invention, the content of the repeating unit structurerepresented by the general formula (4) is preferably within the range of0.01 to 99 mol %, more preferably within the range of 1 to 90 mol % onthe basis of the whole block polymer. When the above content is withinthe range of 0.01 and 99 mol %, carboxylic acid moieties can interact sowell with each other that they may function sufficiently, which ispreferable. Furthermore, the content of the repeating unit structure onthe basis of the block segment is generally 5 mol % or more, preferably20 mol % or more, more preferably 50 mol % or more, and further morepreferably 80% or more, and the content may also be 100 mol %. The ratioof the polyalkenyl ether repeating unit structure in the block polymerof the present invention is preferably 50 mol % or more, and morepreferably 80 mol %, and may also be 100 mol % in the block polymerexcept for both terminal portions.

The number-average molecular weight (Mn) of the block polymer of thepresent invention is not less than 200 but no more than 10,000,000, andthe range preferably used is not less than 1,000 but no more than1,000,000. When the number-average molecular weight is not less than 200but no more than 10,000,000, it causes less entanglement or twisting ina polymer chain or between polymer chains, so that the polymer is easilydispersed in a solvent and can sufficiently exhibit the steric effect asa polymer.

The polymerization degree of each block segment is preferably not lessthan 3 but no more than 10,000, more preferably not less than 5 but nomore than 5,000, and most preferably not less than 10 but no more than4,000.

Further, in order to improve the dispersion stability and the inclusionproperty (encapsulation property), it is preferable that the molecularmotion of the block polymer is more flexible. This is because when themolecular motion of the block polymer is flexible, the block polymereasily becomes entangled (or intertwined) physically with the surface ofa functional substance to have a high affinity therewith, and alsobecause a coating layer is easily formed on a recording medium. On thisaccount, the glass transition temperature Tg of the main chain of theblock polymer is preferably 20° C. or less, more preferably 0° C. orless, and further more preferably −20° C. or less. In this respect also,the polymer having a polyvinyl ether structure is preferably usedbecause it generally has a low glass transition temperature and flexiblecharacteristics. In the above described examples of the repeating unitstructures, their glass transition temperature is approximately −20° C.or less in most cases.

In a preferred embodiment, the block polymer of the present invention isan amphiphilic polymer. Because of its amphiphilicity, the block polymereasily takes a micellar structure, whereby it includes functionalsubstances in the core portion of the micelle or adsorbs the substancesto the hydrophobic portion thereof, so that the functional substancescan be well dispersed in the block polymer. When at least one blocksegment is solvophobic and at least one block segment is solvophilic inthe block polymer of the present invention, amphiphilicity develops. Asa solvent with regard to which the solvophobicity and solvophilicity areexhibited, an aqueous solvent is preferably used. In other words, theblock polymer of the present invention preferably has at least onehydrophobic segment and at least one hydrophilic segment. For example,the hydrophobic segment is a structure represented by the generalformula (8) wherein R¹ is an alkyl group or phenyl group, and thehydrophilic segment is a structure represented by the general formula(3). Moreover, with the block polymer of the present invention, it isalso possible to form an amphiphilic structure that is based onproperties of fluorophilicity and fluorophobicity, as well as beingbased on the amphiphilicity in terms of hydrophilicity andhydrophobicity. It is possible to form in an organic solvent such amicellar structure that fluorophilic segments form a core andfluorophobic and organic-solvent-philic segments are located outsidethereof. The repeating unit structure represented by the general formula(4) is used as a main repeating unit structure in the fluorophilicsegment.

Polymerization of the block polymer of the present invention is mainly acationic polymerization. Examples of an initiator used herein include aprotonic acid such as hydrochloric acid, sulfuric acid, methanesulfonicacid, trifluoroacetic acid, trifluoromethanesulfonic acid or perchloricacid, or a combination of a Lewis acid such as BF₃, AlCl₃, TiCl₄, SnCl₄,FeCl₃, RAlCl₂ or R_(1.5)AlCl_(1.5) (wherein R represents alkyl), with acation source (wherein examples of such a cation source include aprotonic acid, and an adduct obtained from water, alcohol, vinyl etherand a carboxylic acid). By making such an initiator coexist with thepolymeric compound (monomer), a polymerization reaction will proceed tosynthesize the block polymer.

A polymerization method that is more preferably used in the presentinvention will be explained below. There have been many reports onmethods of synthesizing a polymer containing a polyvinyl etherstructure. Among others, the cationic living polymerization methodaccording to Aoshima et al. is representative (Polymer Bulletin Vol. 15,1986, p.417; and Japanese Patent Application Laid-Open Nos. H11-322942and H11-322866). By synthesizing a polymer by the cationic livingpolymerization, various polymers such as a homopolymer, copolymerconsisting of two or more component monomers, as well as block polymer,graft polymer, graduation polymer, and the like can be synthesized whilemaking their lengths (molecular weights) equal. Moreover, the livingpolymerization can also be carried out with an HI/I₂ system or HCl/SnCl₄system.

The fifth feature of the present invention will be described. The fifthfeature of the present invention relates to a block polymer having atleast three block segments, two segments of which are solvophobic andsolvophilic, and another segment of which has a repeating unit structurehaving a fluorine-substituted aromatic structure therein. The aboveblock segment of the block polymer of the present invention, which has arepeating unit structure having a fluorine-substituted aromaticstructure, preferably has solvophilicity or fluorophilicity. The term“fluorophilicity” has a meaning extremely close to the meaning thatother segments have fluorophobicity. Namely, this is similar to the factthat as for the hydrophobicity, the hydrophobic interaction isexhibited, not based on affinity between hydrophobic groups, but as aresult of exclusion from the affinity between hydrophilic groups. Thus,the term “fluorophilicity” will be herein employed although not based onaffinity between fluorophilic groups. When a block segment having arepeating unit structure having a fluorine-substituted aromaticstructure is fluorophilic, it means that the block polymer has segmentswith three different properties such as solvophilicity, solvophobicityand fluorophilicity. Accordingly, it becomes possible for the blockpolymer to form a specific microphase separated structure, to form aspecific micellar structure, or to include a fluorophilic functionalsubstance, which, in general, is difficult to disperse. The same holdsgood of the polymer compound of the fourth feature of the presentinvention.

Moreover, in a block polymer as another preferred example of the fifthfeature of the present invention, wherein a block segment having arepeating unit structure with a fluorine-substituted aromatic structureis solvophilic, it is particularly preferable that the repeating unitstructure with a fluorine-substituted aromatic structure has at leastone selected from a carboxylic acid, a carboxylic acid ester and acarboxylic acid salt therein. Thereby, the dissociative property of thecarboxylic acid is extremely enhanced, so as to secure the highdispersion stability in an aqueous solvent that is preferably used.

As with the above-described features of the present invention, the aboveblock polymer of the fifth feature of the present invention preferablycomprises a polyalkenyl ether repeating unit structure, and morepreferably consists of polyalkenyl ether repeating unit structures. Inthe present invention, specific examples of block polymers comprising apolyalkenyl ether unit structure are included. With the sixth feature ofthe present invention, there is provided a block polymer having at leastthree or more block segments, two segments of which are solvophobic andsolvophilic, and another segment of which has a repeating unit structurehaving a fluorine-substituted aromatic structure therein. Thereby, thepolymer, and a polymer composition and a recording material using thepolymer exhibit extremely good characteristics. For example, in the caseof using a block polymer in accordance with a particularly preferredembodiment, whose block segment having a repeating unit structure havinga fluorine-substituted aromatic structure is solvophilic, extremelyexcellent weather resistance and fixability can be realized, asdescribed below. It is, of course, preferable to exhibit thesecharacteristics. However, the present invention is not particularlylimited to the presence of a polyalkenyl ether main chain and ischaracterized by a block polymer having at least three block segments,in which two block segments are solvophobic and solvophilic and anotherblock segment has a repeating unit structure with a fluorine-substitutedaromatic structure therein. Accordingly, examples of the polymer mainchain structure further include acryl, methacryl, styryl and maleyl.

The polyalkenyl ether repeating unit structure represented by thegeneral formula (4) is a specific example of the repeating unitstructure having a fluorine-substituted aromatic structure, which ispreferably used. Specific examples of such a repeating unit structureare also the same as those listed above.

Moreover, a specific example of a repeating unit structure used forblock segments other than the above mentioned is a compound containing arepeating unit represented by the following general formula (9):

wherein A represents a polyalkenyl group which may be substituted; Grepresents any structure selected from —O—, —OCO—, —COO— and —CONR¹—; R¹represents a hydrogen atom or a linear or branched alkyl group of 1 to 3carbon atoms which may be substituted; 1 represents an integer of 0 or1; each J represents independently a linear or branched alkyl or alkenylgroup of 1 to 15 carbon atoms which may be substituted, in whichmethylene group(s) in the alkyl or alkenyl group may be displaced byoxygen atom(s) or aromatic ring(s), and hydrogen atom(s) attached tocarbon atom(s) in the alkyl or alkenyl group may be displaced byhydroxyl group(s); and m represents an integer of 0 to 30.

Specific examples of the repeating unit structure represented by thegeneral formula (9) are as follows:

In the above examples, Ph represents a phenylene or phenyl group.

Moreover, the block polymer of the present invention can also comprise asegment that causes a phase change from hydrophilic to hydrophobic orfrom hydrophobic to hydrophilic in response to stimulation such as achange in temperature, exposure to electromagnetic waves, a change inpH, or a change in concentration, which is preferable. The block polymercompound of the present invention is a block polymer having at leastthree block segments. The block polymer compound has at least oneselected from a carboxylic acid, a carboxylic acid ester and acarboxylic acid salt, and at least one fluorine atom, in a side chain ofat least one segment of the block polymer, and one of the block segmentsmay be a stimulus responsive block segment. The stimulation ispreferably a change in temperature, exposure to electromagnetic waves, achange in pH, or a change in concentration, and these stimulations mayalso be used in combination. An ABC triblock polymer described below isa specific example of the block polymer of the present invention havingstimulus responsibility, to which the present invention is, however, notlimited. The ABC triblock polymer comprises the following block segmentA exhibiting hydrophobicity,

as an example of the most solvophobic repeating unit, the followingblock segment C having a carboxylic acid group and exhibitinghydrophilicity,

as an example of the most solvophilic repeating unit having an ionicfunctional group and fluorine atoms, and the following nonionichydrophilic block segment B that is responsive to stimulation bytemperature and has a smaller hydrophilicity than the hydrophilicity ofthe above segment C,

as an example of the other repeating unit. Incidentally, the abovehydrophilic segment B is a block segment that is responsive tostimulation by temperature and is known to causes a phase change suchthat it is hydrophobic at a temperature of about 70° C. or more andbecomes hydrophilic at a temperature less than that temperature, whichhas also been confirmed by differential scanning calorimetry (DSC).

As with the fourth feature of the present invention, in the fifthfeature of the present invention, an amphiphilic block having an alkenylether structure as a repeating unit is used which has at least oneselected from an aromatic structure, an aromatic carboxylic acid, anaromatic carboxylic acid ester and an aromatic carboxylic acid salt eachhaving hydrogen atom(s) displaced by fluorine atom(s), in a side chainof at least one block segment. Accordingly, a higher order elaboratedstructure can be formed. In addition, by imparting similar properties tomultiple block segments, it makes also possible to stabilize theproperties. For example, when a dispersion liquid is prepared using theabove-described amphiphilic block polymer and using a coloring materialand water as a solvent, it is possible to include the coloring materialin a micelle formed by the block polymer. Thus, a coloringmaterial-included ink composition can easily be formed. Moreover, theparticle diameters of the particles of the dispersion composition canalso be made very uniform. Furthermore, the dispersion state can be madeextremely stable. As meaning for confirming the inclusion state, the inkcomposition is subjected to Energy-filtered transmission electronmicroscopy (EFTEM) observation using a cryotransfer system to observespherical micelles, and the sample is subjected to elementary analysiswith electron energy loss spectroscopy (EELS) to confirm the inclusionof the coloring material. Further, if a release of functional substancescan be confirmed under micelle disruption conditions, then the inclusionstate can be indirectly confirmed.

The sixth feature of the present invention is a composition comprisingany one of the above described polymer compounds. The composition of thepresent invention preferably contains any one of the above describedpolymers compounds, a coloring material, a functional substance having apredetermined useful function, and a solvent or dispersion medium. Thepolymer compound can preferably be used to well disperse the coloringmaterial, the functional substance or the like. It is also possible touse a pigment, metal, herbicide, insecticide, or biological materialsuch as a medicine. In addition, the above polymers of the presentinvention may also be used as good water-soluble polymer compounds.Further, since the polymers can also be used as adhesives or tackingagents, the polymers do not always need to contain a functionalsubstance.

The functional substance may preferably be used in an amount of 0.1 to50 mass % based on the total mass of the composition of the presentinvention. Further, it may also be a soluble substance, and dyes,molecular catalysts, and the like may also be used as the functionalsubstance.

Moreover, the polymer compound is preferably contained in thecomposition of the present invention in an amount of 0.5 to 98 mass %based on the total mass of the composition.

A preferred example of the composition of the present invention may be arecording material containing a solvent or dispersion medium, a coloringmaterial and the above-mentioned polymer compound. Specific examples ofsuch a recording medium may be a toner composition containing adispersion medium such as a binder resin, a coloring material and theabove-mentioned polymer compound, and an ink composition containing asolvent, a coloring material and the above polymer compound.

An ink composition that is a preferred embodiment of the presentinvention will be described below.

The content of the above-described polymer compound in the inkcomposition of the present invention is within the range of 0.1 to 90mass %, preferably 1 to 80 mass %. When used for ink-jet. printers, thecontent of the polymer compound is preferably within the range of 1 to30 mass %.

Next, components other than the above-mentioned polymer compoundscontained in the ink composition of the present invention will bedescribed in detail below. Examples of other components include organicsolvents, water, water-soluble solvents, coloring materials andadditives.

[Organic Solvents]

Examples of the organic solvent include hydrocarbons solvent, aromaticsolvents, ether solvents, ketone solvents, ester solvents and amidesolvents.

[Water]

As water, ion exchange water, pure water and extra pure water whereinmetal ions are eliminated are preferable used in the present invention.

[Aqueous Solvents]

Examples of the aqueous solvent used in the invention include:polyvalent alcohols such as ethylene glycol, diethylene glycol,triethylene glycol, polyethylene glycol, propylene glycol, polypropyleneglycol or glycerol; polyvalent alcohol ethers such as ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, ethylene glycolmonobutyl ether, diethylene glycol monoethyl ether or diethylene glycolmonobutyl ether; and nitrogen-containing solvents such asN-methyl-2-pyrrolidone, substituted pyrrolidone or triethanolamine. Inaddition, monovalent alcohols such as methanol, ethanol or isopropylalcohol can also be used to accelerate the drying of an aqueousdispersion on a recording medium.

The total content of the organic solvent, water and aqueous solventdescribed above is preferably within the range of 20 to 95 mass %, morepreferably 30 to 90 mass % based on the total mass of the inkcomposition of the present invention.

[Coloring Materials]

Coloring materials such as pigments or dyes may be contained in the inkcomposition of the present invention with pigments being more preferablyused.

Specific examples of the pigments and dyes used in the ink compositionare as follows.

The pigments may be either organic or inorganic pigments. A blackpigment and pigments of three primary colors, cyan, magenta and yellowmay preferably be used for the ink. Incidentally, color pigments otherthan those described above, colorless or pale-color pigments, metallicluster pigments, and the like may also be used. Moreover, pigments whichhave been newly synthesized for the present invention may also be used.

Examples of commercially available black, cyan, magenta and yellowpigments are shown below.

Examples of the black pigment include, but are not limited to, Raven1060 (manufactured by Colombian Carbon Co.), MOGUL-L (manufactured byCabot Corp.), Color Black FW1 (manufactured by Degussa AG) and MA100(manufactured by Mitsubishi Chemical Corp.)

Examples of the cyan pigment include, but are not limited to, C.I.Pigment Blue-15: 3, C.I. Pigment Blue-15: 4 and C.I. Pigment Blue-16.

Examples of the magenta pigment include, but are not limited to, C.I.Pigment Red-122, C.I. Pigment Red-123 and C.I. Pigment Red-146.

Examples of the yellow pigment include, but are not limited to, C.I.Pigment Yellow-74, C.I. Pigment Yellow-128 and C.I. Pigment Yellow-129.

Moreover, pigments self-dispersible in water may also be used for thecomposition of the present invention. Such pigments dispersible in waterinclude those of which dispersibility is enhanced utilizing a sterichindrance effect of a polymer adsorbed onto the surface thereof, or anelectrostatic repulsion. Examples of such pigments that are commerciallyavailable include CAB-0-JET200, CAB-0-JET300 (both manufactured by CabotCorp.), and Microjet Black CW-1 (manufactured by Orient Chemical Corp.).

The pigments used for the ink composition of the present invention arepreferably contained in the amount of 0.1 to 50 mass % based on thetotal mass of the ink composition. If the content of pigment is lessthan 0.1 mass %, a sufficient image density cannot be obtained. Incontrast, if the content of the pigment is more than 50 mass %, thefixation property of an image may be lowered. The content of the pigmentis more preferably within the range of 0.5 to 30 mass %.

Furthermore, the dyes may also be used for the ink composition of thepresent invention. Direct dyes, acid dyes, basic dyes, reactive dyes,water-soluble dyes for food pigments, insoluble pigments as dispersedye, and fat-soluble dyes can be used, which will be described below.

Examples of the water-soluble dyes include direct dyes such as C.I.Direct Black -17, -62 and -154, C.I. Direct Yellow -12, -87 and -142,C.I. Direct Red -1, -62 and -243, C.I. Direct Blue -6, -78 and -199,C.I. Direct Orange -34 and -60, C.I. Direct Violet -47 and -48,-C.I.Direct Brown -109, and C.I. Direct Green -59;

acid dyes such as C.I. Acid Black -2, -52 and -208, C.I. Acid Yellow-11, -29 and -71, C.I. Acid Red -1, -52 and -317, C.I. Acid Blue -9, -93and -254, C.I. Acid Orange -7 and -19, and C.I. Acid Violet -49;

reactive dyes such as C.I. Reactive Black -1, -23 and -39, C.I. ReactiveYellow -2, -77 and -163, C.I. Reactive Red -3, -111 and -221, C.I.Reactive Blue -2, -101 and -217, C.I. Reactive Orange -5, -74 and -99,C.I. Reactive Violet -1, -24 and -38, C.I. Reactive Green -5, -15 and-23, and C.I. Reactive Brown -2, -18 and -33; and

other dyes such as C.I. Basic Black -2, C.I. Basic Red -1, -12 and -27,C.I. Basic Blue -1 and -24, C.I. Basic Violet -7, -14 and -27, C.I. FoodBlack -1 and -2.

Examples of the fat-soluble dyes include the following commerciallyavailable products for each color.

Examples of the black fat-soluble dye include C.I. Solvent Black -3,-22: 1 and -50, but not limited thereto.

Examples of the yellow fat-soluble dye include C.I. Solvent Yellow -1,-25: 1 and -172, but not limited thereto.

Examples of the orange fat-soluble dye include C.I. Solvent Orange -1,-40: 1 and -99, but not limited thereto.

Examples of the red fat-soluble dye include C.I. Solvent Red -1, -111and -229, but not limited thereto.

Examples of the violet fat-soluble dye include C.I. Solvent Violet -2,-11 and -47, but not limited thereto.

Examples of the blue fat-soluble dye include C.I. Solvent Blue -2, -43and -134, but not limited thereto.

Examples of the green fat-soluble dye include C.I. Solvent Green -1, -20and -33, but not limited thereto.

Examples of the brown fat-soluble dye include C.I. Solvent Brown -1, -12and -58, but not limited thereto.

The above-described examples of the coloring materials are preferablefor the ink of the present invention, but coloring materials used forthe ink composition of the present invention are not particularlylimited to the above-described coloring materials. The dye used for theink composition of the present invention is preferably contained in theamount of 0.1 to 50 mass % based on the total mass of the ink.

[Additives]

Various additives or auxiliary agents can be added as needed to thecomposition of the present invention. One of such additives is adispersion stabilizer, which stably disperses a pigment in a solvent.The composition of the present invention comprises a polymer having apolyvinyl ether structure, so that it has a function to disperse agranular solid such a pigment. When dispersion is insufficient, however,other dispersion stabilizers may be added.

As other dispersion stabilizers, resins having both hydrophilic andhydrophobic parts, or surfactants can be used. A copolymer consisting ofa hydrophilic monomer and a hydrophobic monomer is an example of such aresin having both hydrophilic and hydrophobic moieties.

Examples of such a hydrophilic monomer include acrylic acid, methacrylicacid, maleic acid, fumaric acid, the above described carboxylic acidmonoesters, vinylsulfonic acid, styrenesulfonic acid, vinyl alcohol,acrylamide and methacryloxyethyl phosphate. Examples of such ahydrophobic monomer include styrene, styrene derivatives such asα-methylstyrene, vinylcyclohexane, vinylnaphthalene derivatives, acrylicacid esters and methacrylic acid esters. Copolymers with variousstructures, such as a random copolymer, block copolymer or graftcopolymer, may be used. Naturally, hydrophilic and hydrophobic monomersused herein are not limited to the above-described examples.

Examples of the surfactant to be used include anionic, nonionic,cationic and amphoteric surfactants. Examples of the anionic surfactantinclude a fatty acid salt, alkyl sulfate, alkylaryl sulfonate,alkyldiaryl ether disulfonate, dialkyl sulfosuccinate, alkyl phosphate,naphthalenesulfonic acid formalin condensate, alkyl polyoxyethylenephosphate, and glycerol borate fatty acid ester. Examples of thenonionic surfactant include polyoxyethylene alkyl ether, apolyoxyethyleneoxy propylene block copolymer, sorbitan fatty acid ester,glycerin fatty acid ester, polyoxyethylene fatty acid ester,polyoxyethylene alkylamine, a fluorine-based surfactant, and asilicon-based surfactant. Examples of the cationic surfactant include analkylamine salt, a quaternary ammonium salt, an alkylpyridinium salt,and an alkylimidazolium salt. Examples of the amphoteric surfactantinclude alkyl betaine, alkylamine oxide and phosphatidylcholine. Inaddition, surfactants are also not limited to the above examples.

Further, an aqueous solvent may be added, as needed, to the compositionof the present invention. In particular, when the composition is usedfor an ink for ink jetting, such an aqueous solvent is used also toprevent drying of the ink at a nozzle portion and consolidation of theink. The aqueous solvent can be used singularly or in combination. Theabove listed examples of aqueous solvents can be used as such. In thecase of an ink, the content of the aqueous solvent is within the rangeof 0.1 to 60 mass %, preferably 1 to 40 mass % based on the total massof the ink.

When the composition is used for ink, examples of other additivesinclude a pH adjuster used to stabilize the ink and to achieve stablepiping of the ink in a recording apparatus; a penetrant used to promotethe penetration of the ink into a recording medium so as to hastenapparent drying; a fungicide used to prevent generation of molds in theink; a chelating agent used to block metal ions in the ink so as toprevent deposition of the metal at a nozzle portion or deposition ofinsoluble matters in the ink; an antifoaming agent used to prevent thegeneration of bubbles during the circulation or movement of a recordingliquid or the production of the recording liquid; an antioxidant; afungicide; a viscosity adjuster; an electric conductive agent; and anultraviolet absorber.

To prepare the ink composition of the present invention, the aboveconstituents are mixed, and they are uniformly dissolved or dispersed.For example, a plurality of components are mixed, and the mixture isgrounded and dispersed with a sand mill, ball mill, homogenizer ornanomiser to prepare an ink mother liquid, and solvents or additives areadded thereto to adjust physical properties, thereby producing the inkcomposition of the present invention.

Subsequently, the toner composition of the present invention will bedescribed below. Specifically, the toner composition comprises adispersion medium such as a binder resin, a coloring material and theabove-described polymer compound.

The content of the polymer compound in the toner composition of thepresent invention is generally within the range of 0.1 to 95 mass %, andpreferably within the range of 0.5 to 80 mass %.

Moreover, the polymer compound of the present invention can be usedalone as a binder resin, or it can also be used in combination withanother binder resin such as a styrene acrylic resin or polyester resin.

Subsequently, components other than the polymer compound to be containedin the toner composition of the present invention will be described indetail. Examples of the other components include a binder resin, acoloring material (pigment or dye), a charge controlling agent, a moldrelease agent, an external additive and a magnetic particle.

(Addition of Other Components to Toner Composition)

Examples of the binder resin include a styrene acrylic copolymer,polyester and polycarbonate. The content of such a binder resin ispreferably 10 to 99 mass %. As the coloring material the pigments ordyes described for the above ink composition can be used. The content ofsuch a coloring material is 0.1 to 50 mass %. Examples of the chargecontrolling agent include a metal-azo complex, a triphenylmethane dye,nigrosine and an ammonium salt. The content of the antistatic agent is0.1 to 30 mass %. Examples of the mold release agent include a syntheticwax and a natural wax. Examples of the external additive includeinorganic fine particles such as silica, alumina or titania, and resinfine particles such as polyvinylidene fluoride (PVDF) orpolytetrafluoroethylene. Examples of the magnetic particle includemagnetite, hematite and ferrite. The toner composition can function evenwhen it does not contain all the above components, and may furthercontain components other than those described above.

In order to prepare the toner composition of the present invention, forexample, the above-described components are mixed, melted and kneaded,so as to obtain a homogeneous mixture, which mixture is then groundedwith a speed mill or jet mill, and the obtained particles are classifiedby size, so as to obtain toner with a desired size. The externaladditive may be added to the toner, and the mixture is mixed with amixer, so as to obtain the toner composition of the present invention.

Next, the image formation method, liquid application method, and imageformation apparatus that use the composition of the present inventionwill be described.

[Image Formation Method, Liquid Application Method, and Apparatus]

The composition of the present invention can be used for various typesof image formation methods and apparatuses, such as variousprinting,methods, ink-jet methods or electrophotography. An image can beprinted by the above image formation method using the above apparatus.Further, when using the liquid composition, a fine pattern can be formedby the ink-jet method, or such a liquid composition can be used for theliquid application method including administration of a medicine or thelike.

The image formation method of the present invention is a method offorming an excellent image using the composition of the presentinvention. The image formation method of the present invention ispreferably a method of discharging the ink composition of the presentinvention from an ink discharge unit to deposit it on a recordingmedium, thereby effecting recording. As the image formation method, theink-jet method is preferably used which imparts a thermal energy to theink to discharge the ink.

As the ink-jet printer using the ink-jet ink composition of the presentinvention, there are used various ink-jet recording apparatuses such asa piezo ink-jet system recording apparatus using a piezoelectricelement, or a bubble jet (registered trademark) system in which athermal energy is imparted to an ink to generate a bubble, thusperforming recording.

The overview of the ink-jet recording apparatus will be explained below,referring to. FIG. 1. However, FIG. 1 is only an example of thestructure, and it is not intended to limit the present invention.

FIG. 1 is a block diagram showing a structure of the ink-jet recordingapparatus.

FIG. 1 shows a case where a head is moved to perform recording on arecording medium. In FIG. 1, an X direction drive motor 56 and a Ydirection drive motor 58, which drive a head 70 in X and Y directions,are connected to a CPU 50 for controlling the entire movement of therecording apparatus via an X motor drive circuit 52 and a Y motor drivecircuit 54, respectively. In accordance with instructions from the CPU,the X direction drive motor 56 and the Y direction motor drive motor 58are driven via the X motor drive circuit 52 and the Y motor drivecircuit 54, so that the location of the head 70 on the recording mediumis determined.

As shown in FIG. 1, not only the X direction drive motor 56 and the Ydirection motor drive motor 58, but also a head drive circuit 60 isprovided to be connected to the head 70. The CPU 50 controls the headdrive circuit 60 to drive the head 70, that is, to discharge the ink-jetink. Moreover, an X encoder 62 and a Y encoder 64, which detect thelocation of the head, are connected to the CPU50, and the informationregarding the location of the head is inputted in the encoders.Furthermore, a control program is also inputted in a program memory 66.The CPU 50 moves the head 70, based on the control program and theinformation regarding the location from the X encoder 62 and the Yencoder 64, so that the head is positioned at a desired location on therecording medium and the ink-jet ink is then discharged. Thus, a desiredimage can be formed on the recording medium. Further, in the case of animage recording apparatus that can be equipped with multiple ink-jetinks, the above operation is carried out for each ink-jet ink a givennumber of times, so that a desired image can be formed on the recordingmedium.

Further, after the ink-jet ink has been discharged, the head 70 may bemoved, as needed, to a location where an ink removal means (not shown inthe figure) for removing an excess ink attached to the head is provided,and the head 70 may be cleaned by wiping or the like. As specificcleaning methods, the conventional cleaning methods can be used as such.

After completion of the formation of the image, the recording medium onwhich the image has been formed is replaced with a new recording mediumby a carrying mechanism for recording media, which is not shown in thefigure.

It is to be noted that in the present invention, the above-describedembodiment can be changed or modified without departing from the spritor scope of the invention. For example; although the head 70 is moved inthe X-Y axes directions in the above explanation, the head 70 may bemoved only in the X axis direction (or Y axis direction) while therecording medium may be moved in the Y axis direction (or X axisdirection), and thus, the head and the recording medium may be movedrelative to each other to form an image.

The present invention especially exhibits excellent effects when appliedto a head that has a means (for example, an electrothermal transducer,laser beam, etc.) for generating a thermal energy, which is utilized todischarge an ink-jet ink, and discharges the ink-jet ink using thethermal energy. Such an ink-jet system enables formation of a finerimage. By using the ink-jet ink composition of the present invention, amore excellent image can be printed.

As the representative structure or principle of the apparatus having theabove heat energy-generating means, basic principles disclosed in U.S.Pat. Nos. 4,723,129 and 4,740,796 are preferably used. This system canbe applied to both the so-called on-demand type and continuous type. Itis particularly effective to apply this system to the on-demand type.This is because, in the case of the on-demand type, at least one drivingsignal, which corresponds to a discharging information and gives a rapidincrease in temperature that exceeds nuclear boiling, is applied to anelectrothermal transducer located corresponding to a liquid path thatretains liquid, so that a thermal energy is generated from theelectrothermal transducer, thereby causing film boiling on a heat actingsurface of the head, whereby an air bubble can be formed in the liquidin a one-to-one correspondence with the driving signal. By the growthand shrinkage of the air bubble, liquid is discharge via a dischargingopening to form at least one ink droplet. If this driving signal is of apulse-shape, the growth and shrinkage of a air bubble is carried outrapidly and appropriately, so that liquid discharge that is particularlyexcellent in signal-responsibility can be achieved, which is morepreferable. As such a pulse-type driving signal, those described in U.S.Pat. Nos. 4,463,359 and 4,345,262 are appropriate. In addition, withregard to the above-described rate of raise in the temperature of theheat acting surface, when the conditions described in U.S. Pat. No.4,313,124 are adopted, more excellent ink discharge can be carried out.

With regard to the structure of the head, not only the combinedstructure (a linear liquid path or right angle liquid path) consistingof a discharge port, a liquid path and an electrothermal transducer thatis described in each of the above specifications, but the structure thata heat acting unit is located in a bending region, described in U.S.Pat. Nos. 4,558,333 and 4,459,600, are also included in the presentinvention. In addition, the structure in which multiple electrothermaltransducers use a common slit as a discharging unit, described inJapanese Patent Application Laid-Open No. S59-123670, or the structurein which an opening port for absorbing the pressure wave of thermalenergy corresponds to the discharging unit, described in Japanese PatentApplication Laid-Open No. S59-138461, is also effective for the presentinvention. This is to say, regardless of the form of the head, anink-jet ink can be reliably and efficiently discharged according to thepresent invention.

Moreover, the present invention can also be effectively applied to afull line-type head having a length corresponding to the maximum widthof a recording medium in the image formation apparatus of the presentinvention. The structure of such a head may be either a structuresatisfying the above length by a combination of multiple heads, orstructure as a single-piece head.

In addition, the present invention is also effective for a serial typehead, a head fixed to the main body of an apparatus, or an exchangeablechip type head which is equipped in the main body of an apparatus,thereby enabling electric connection with the main body or ink supplyfrom the main body.

Furthermore, the apparatus of the present invention may further comprisea droplet removal means. When such a means is added to the apparatus,further excellent discharging effects can be realized.

Still further, preliminary assisting means is preferably added to theapparatus of the present invention to further stabilize the effects ofthe present invention. Specific examples of such assisting means includea capping means for the head, a pressurizing or sucking means, apreliminary heating means for performing-heating using an electrothermaltransducer, other heating elements or a combination thereof, andpreliminary discharging means for performing discharge other than thedischarge of an ink.

The above film boiling system is the most effective for the presentinvention.

In the apparatus of the present invention, the amount of the ink-jet inkdischarged from each discharging port of the discharge head ispreferably within the range of 0.1 to 100 picolitre.

Still further, the ink composition of the present invention can also beused for an indirect recording apparatus using a recording systemwherein an ink is printed on an intermediate transfer member and thentransferred on a recording medium such as a paper sheet. Further, theink composition of the present invention can also be applied to anapparatus using a direct recording system wherein such an intermediatetransfer member is used.

EXAMPLES

The present invention will be described in detail in the followingexamples. However, these examples are not intended to limit the scope ofthe present invention.

Example 1 Synthesis of CH₂═CHOCH₂CH₂OPh(4F)COOC₂H₅

25 parts by mass of pentafluorobenzoic acid ethyl ester and 21.6 partsby mass of NaNO₂ were mixed in 200 parts by mass of DMSO, and themixture was heated. After the mixture was stirred at 50° C. for 2 hours,it was cooled to room temperature, and 520 parts by mass of ice waterwas added thereto. Concentrated hydrochloric acid was added to themixture to adjust pH to 2, and the mixture was then heated to 100° C.followed by stirring for 30 minutes. The mixture was cooled to roomtemperature followed by extraction with ether. Organic layers werewashed with water and dried with anhydrous magnesium sulfate. Thesolvent was removed, and the obtained residue was washed with hexane toobtain 4-hydroxy-2,3,5,6-tetrafluorobenzoic acid ethyl ester. 200 partsby mass of the obtained 4-hydroxy-2,3,5,6-tetrafluorobenzoic acid ethylester was dissolved in 500 parts by mass of DMF, and an equivalentamount of NaH was gradually added thereto followed by stirring for 1hour. 20 parts by mass of tetrabutylammonium iodide was added thereto,180 parts by mass of 2-chloroethyl vinyl ether was then added thereto,and the thus obtained mixture was stirred at 100° C. for 10 hours. Aftercooling to room temperature, the reaction solution was added to 4,600parts by mass of ice water followed by extraction with ethyl acetate.Organic layers were washed with water and dried with anhydrous magnesiumsulfate. The solvent was removed, and the residue was subjected tosilica gel column chromatography to obtain the objective polymericcompound. The NMR of the thus obtained polymeric compound is shown inFIG. 2.

Example 2 Synthesis of Polymer

0.1 mol of the polymeric compound obtained in Example 1, 0.001 mol ofwater and 0.005 mol of ethyl aluminum dichloride were subjected tocationic polymerization in anhydrous toluene.

After 20 hours the reaction was completed, and methylene chloride andwater were added to the reaction product, and the mixture was washedwith water and then with diluted hydrochloric acid, and further washedwith alkali. Thereafter, the thus washed product was dried withanhydrous sodium sulfate, and the solvent was removed to obtain a highmolecular compound (polymer). The number-average molecular weight of thepolymer measured by the size exclusion chromatography was 2,500.

Example 3 Synthesis of CH₂═CHO(CH₂CH₂O)₂Ph(4F)COOC₂H₅

The synthesis was carried out in the same manner as in Example 1 withthe exception that CH₂═CHOCH₂CH₂OCH₂CH₂OTs (wherein Ts represents atosyl group) was used instead of 2-chloroethyl vinyl ether of Example 1to obtain the objective polymeric compound.

Example 4

Using each polymeric compound obtained in Example 3, the polymerizationwas carried out in the same manner as in Example 2 to obtain a polymercompound. The number-average molecular weight of the polymer compoundmeasured by the size exclusion chromatography was 1,800.

Example 5

The high molecular compound (polymer) synthesized in Example 2 was mixedwith a 5N aqueous sodium hydroxide solution, and the mixture was stirredat room temperature (23° C.) for 40 hours, so that ester was hydrolyzed.The solution was neutralized with 5N hydrochloric acid, extracted withmethylene chloride, and dried. Thereafter, the solvent was removed toobtain a free carboxylic acid polymer. The obtained polymer wasneutralized with an equivalent amount of 1N sodium hydroxide, and waterwas than removed to obtain a sodium carboxylate polymer.

Example 6

2 parts by mass of pigment (product name: Mogul L, manufactured by CabotCorp.), 3 parts by mass of the sodium carboxylate polymer of Example 5,and 25 parts by mass of diethylene glycol were added to 177 parts bymass of ion exchange water, followed by dispersion with an ultrasonichomogenizer. The dispersion solution was subjected to pressurefiltration using 1 μm filter to prepare an ink composition. The pigmenthad good dispersibility.

Example 7 Synthesis of CH₂═CHOCH₂CH₂OPh(2F)COOC₂H₅ wherein two fluorineatoms are substituted at positions 3 and 5 of benzoic acid

The objective compound was synthesized using HOPh(2F)COOC₂H₅ in the samemanner as in Example 1. Using the obtained compound, a polymer wassynthesized in the same manner as in Example 2.

Example 8

Using the ink composition prepared in Example 6, ink-jet recording wascarried out. An ink tank of a bubble jet (registered trademark) printer(product name: BJJ-800J) manufactured by Canon Inc. was filled with theink composition of Example 6. Using this ink-jet printer, recording wascarried out on a plain paper sheet. As a result, clear black printingwas achieved.

Example 9

Using the free carboxylic acid polymer that is a precursor of the sodiumcarboxylate polymer obtained in Example 5, a toner composition wasproduced by the following method.

100 parts by mass of polyester resin (bisphenol A, terephthalic acid,n-dodecenylsuccinic acid, trimellitic acid and diethylene glycol weresynthesized at a molar ratio of 20:38:10:5:27), 70 parts by mass ofmagnetite (Fe₃O₄), 3 parts by mass of the above described freecarboxylic acid polymer, 2 parts by mass of triphenylmethane dye, and 3parts by mass of low molecular-weight polypropylene were preliminarilymixed, and the obtained mixture was melted and kneaded with a ruder.After cooling the resultant product, it was roughly grounded with aspeed mill, and then finely grounded with a jet mill. Thereafter, theparticles were classified using a zigzag separator to obtain tonerhaving a volume mean diameter of 11 μm.

0.4 part by mass of positively-charged hydrophobic dry silica treatedwith amino-modified silicon oil (having viscosity at 25° C. of 100 cpand amine equivalence of 800) and 0.2 part by mass of spherical PVDFparticles having a mean particle size of 0.2 μm were added to 100 partsby mass of the above obtained toner. Thereafter, the mixture was blendedwith a Henschel mixer, so as to obtain a positively charged tonercomposition. Using this toner composition, printing was carried out witha printer NP-3525 manufactured by Canon Inc. As a result, clear printingwas achieved.

Example 10 Synthesis of Block Polymer

Synthesis of a diblock polymer consisting of isobutyl ether,CH₂═CHOCH₂CH₂OPhPh:(IBVE-r-VEEtPhPH: A block), and4-(2-vinyloxy)ethoxy-2,3,5,6-tetrafluorobenzonic acid ethyl(VEOEtPh(4F)COOEt: B block)

The inside of a glass container equipped with a three-way cock wassubjected to nitrogen substitution, and adsorbed water was eliminated byheating to 250° C. under a nitrogen gas atmosphere. The system wasreturned to room temperature, and thereafter, 6 mmol (millimole) ofIBVE, 6 mmol of VEEtPhPh, 16 mmol of ethyl acetate, 0.1 mmol of1-isobutoxyethyl acetate, and 11 ml of toluene were added to thereaction system. Thereafter, the reaction system was cooled. When thetemperature in the system was reached 0° C., 0.2 mmol of ethylaluminumsesquichloride (an equimolar mixture consisting of diethylaluminumchloride and ethylaluminum dichloride) was added to the reaction system,so as to initiate polymerization. Molecular weight was monitored bymolecular sieve chromatography (GPC) in a time-division manner, andthus, completion of the polymerization of the A block was confirmed.

Subsequently, 10 mmol of the B block monomer was added thereto, and thepolymerization was continued. 24 hours later, the polymerizationreaction was terminated. The polymerization reaction was terminated byadding 0.3% by mass of ammonia/methanol aqueous solution to the system.The reaction mixture solution was diluted with dichloromethane, and thediluted solution was washed with 0.6 M hydrochloric acid 3 times andthen with distilled water 3 times. The obtained organic layers wereconcentrated and exsiccated with an evaporator, and the obtainedvacuum-dried product was repeatedly dialyzed using a cellulosesemipermeable membrane in a methanol solvent to eliminate monomericcompounds, so as to obtain a diblock polymer of interest. The compoundwas identified by NMR and GPC. As a result, Mn=14,600 and Mw/Mn=1.32.The polymerization ratio (=compositional ratio) was A:B=100:10. Thepolymerization ratio of two types of monomers was 1:1 in the A block.

Thereafter, the thus obtained block polymer was hydrolyzed in a mixedsolution consisting of dimethylformamide and sodium hydroxide water.Thus, the B block components were hydrolyzed, so as to obtain a diblockpolymer that was converted into a sodium salt. The compound wasidentified by NMR and GPC.

Thereafter, the compound was neutralized with 0.1 N hydrochloric acid ina water dispersion solution, so as to obtain a diblock polymer wherein Bcomponents became free carboxylic acids. The compound was identified byNMR and GPC.

[pKa Measurement of B Block]

3.0 mmol of an aliquot was picked up at a monomer unit of the B blockcomponents from the carboxylic acid-type block polymer obtained inExample 10. Then, distilled water was added thereto to obtain 50 g ofaqueous solution in total. A 0.1N aqueous sodium hydroxide solution wasadded to the obtained aqueous solution, and the mixture was measured bypotentiometric titration to obtain pKa. As a result, pKa=2.2. Thetitration was carried out using an automatic titrater “COM-555”(manufactured by Hiranuma Sangyo Co., Ltd.)

Example 11

15 parts by mass of the carboxylic acid salt-type block polymer obtainedin Example 10 and 7 parts by mass of Oil Blue N (C.I. Solvent Blue-14manufactured by Aldridge) were codissolved in 150 parts by mass ofdimethylformamide. The resultant product was converted into an aqueousphase using 400 parts by mass of distilled water, so as to obtain an inkcomposition. Although the obtained ink composition was left for 10 days,the Oil Blue was neither separated nor deposited.

Example 12

The printing head of an ink-jet printer (product name: BJF800,manufactured by Canon Inc.) was filled with the ink prepared in Example11, and recording was carried out. 1 minute after the recording, theprinted portion was strongly scratched 3 times with a line marker, buttailing of blue color did not appear at all. Thus, it was found that theink has extremely good fixability.

Comparative Example 1

2 parts by mass of black self-dispersing pigment (product name:CAB-0-JET300, manufactured by Cabot Corp.), 0.5 part by mass ofsurfactant (Nonion E-230 manufactured by NOF Corp.), 5 parts by mass ofethylene glycol, and 92.5 parts by mass of ion exchange water were mixedto prepare an ink composition. Using the ink composition, recording wascarried out in the same manner as in Example 3. 1 minute after therecording, the printed portion was strongly scratched once with a linemarker. As a result, tailing of black color was observed.

Example 13 Synthesis of Block Polymer

Synthesis of a triblock polymer consisting of isobutyl vinyl ether(IBVE: A block), 2-methoxyethyl vinyl ether (MOVE: B block), and4-(2-vinyloxy)ethoxy-2,3,5,6-tetrafluorobenzoic acid ethyl(VEOEtPh(4F)COOEt: C block)

The inside of a glass container equipped with a three-way cock-wassubjected to nitrogen substitution, and adsorbed water was eliminated byheating to 250° C. under a nitrogen gas atmosphere. The system wasreturned to room temperature, and thereafter, 12 mmol (millimole) ofIBVE, 16 mmol of ethyl acetate, 0.05 mmol of 1-isobutoxyethyl acetate,and 11 ml of toluene were added to the reaction system. Thereafter, thereaction system was cooled. When the temperature in the system wasreached 0° C., 0.2 mmol of ethylaluminum sesquichloride (an equimolarmixture consisting of diethylaluminum chloride and ethylaluminumdichloride) was added to the reaction system to initiate polymerization.Molecular weight was monitored by molecular sieve chromatography (GPC)in a time-division manner, and thus, completion of the polymerization ofthe A block was confirmed.

Subsequently, 12 mmol of MOVE as the B block was added thereto, and thepolymerization was continued. Completion of the polymerization of the Bblock was confirmed by monitoring using GPC. Thereafter, 10 mmol of theC block monomer was added thereto, and the polymerization was continued.24 hours later, the polymerization reaction was terminated. Thepolymerization reaction was terminated by adding 0.3% by mass ofammonia/methanol aqueous solution to the system. The reaction mixturesolution was diluted with dichloromethane, and the diluted solution waswashed with 0.6 M hydrochloric acid 3 times and then with distilledwater 3 times. The obtained organic layers were concentrated andexsiccated with an evaporator, and the obtained vacuum-dried product wasrepeatedly dialyzed using a cellulose semipermeable membrane in amethanol solvent to eliminate monomeric compounds to obtain a triblockpolymer of interest. The compound was identified by NMR and GPC. As aresult, Mn=40,685 and Mw/Mn=1.41. The polymerization ratio wasA:B:C=200:200:30.

Thereafter, the thus obtained block polymer was hydrolyzed in a mixedsolution consisting of dimethylformamide and sodium hydroxide water.Thus, the C block components were hydrolyzed, so as to obtain a triblockpolymer that was converted into a sodium salt. The compound wasidentified by NMR and GPC.

Thereafter, the compound was neutralized with 0.1 N hydrochloric acid ina water dispersion solution to obtain a triblock polymer wherein Ccomponents became free carboxylic acids. The compound was identified byNMR and GPC.

Example 14

15 parts by mass of the carboxylic acid salt-type block polymer obtainedin Example 13 and 7 parts by mass of Oil Blue N (C.I. Solvent Blue-14manufactured by Aldridge) were codissolved in 150 parts by mass ofdimethylformamide. The resultant product was converted into an aqueousphase using 400 parts by mass of distilled water, so as to obtain an inkcomposition. Although the obtained ink composition was left for 10 days,the Oil Blue was neither separated nor deposited.

In addition, encapsulation of the coloring material in the block polymerwas confirmed by EF-TEM observation with a cryotransfer device andelementary analysis with EELS, as stated above. Moreover, 5 samples wereprepared by applying the ink on plain papers, and they were thensubjected to a light resistance test under the outside light forapproximately 2 months, using a light resistance tester Suntest CPS+manufacture by Toyo Seiki). As a result, it was found that all thesamples kept an optical density of 90% or more.

Comparative Example 2

The Oil Blue N (C.I. Solvent Blue-14 manufactured by Aldridge) used inExample 14 was dissolved in THF. In the same manner as in Example 14, 5samples were prepared by applying the ink on plain papers, and they werethen subjected to a light resistance test under the outside light forapproximately 2 months, using a light resistance tester Suntest CPS+manufacture by Toyo Seiki). As a result, it was found that all thesamples had an optical density of less than 75%.

Example 15

The printing head of an ink-jet printer (product name: BJF800,manufactured by Canon Inc.) was filled with the ink prepared in Example14, and recording was carried out. 1 minute after the recording, theprinted portion was strongly scratched 3 times with a line marker, buttailing of blue color did not appear at all. Thus, it was found that theink has extremely good fixability.

Example 16

Water dispersion solutions were prepared, each of which contained 15% byweight of the carboxylic acid ester-type triblock polymer or 15% byweight of the carboxylic acid salt-type triblock polymer that wereobtained in Example 13. Each solution was observed with a polarizingmicroscope. As a result, completely different textures were observedfrom the solutions, and thus, formation of different structures wasobserved.

A water dispersion solution containing 15% by weight of the carboxylicacid ester-type diblock polymer obtained in Example 10 was mixed with awater dispersion solution containing 15% by weight of the carboxylicacid ester-type triblock polymer at a weight ratio of 1:2, and theobtained mixture was observed with a polarizing microscope. As a result,it was found that a texture similar to the texture of the carboxylicacid ester-type triblock polymer was observed but that the intensity oftransmitted light was reduced. It is therefore considered that there wasno change in the basic structure but that a structure with reduced orderparameter was formed.

Example 17

A triblock polymer was synthesized in the same manner as in the case ofthe carboxylic acid ester-type triblock polymer of Example 13 with theexception that 4-(2-vinyloxy)ethoxy-2,3,4,5,6-polyfluorobenzene was usedinstead of 4-(2-vinyloxy)ethoxy-2,3,5,6-tetrafluorobenzoic acid ethyl. Awater dispersion solution containing 15% by weight of the polymer wasprepared, and it was then observed with a polarizing microscope. As aresult, a texture similar to the texture of the carboxylic acidester-type triblock polymer of Example 16, and formation of a similarstructure was observed.

1. An amphiphilic block polymer comprising: (a) a hydrophilic blocksegment having a repeating unit structure represented by the generalformula (4):

wherein: A represents a linear alkylene group of 1 to 15 carbon atoms; mrepresents 0 or 1; B represents a single bond or an alkylene group of 1to 20 carbon atoms; each D represents independently an aromatic ringstructure in which at least one hydrogen atom attached to the ring isdisplaced by a fluorine atom; n represents an integer of 1 to 10; and Rrepresents an alkyl group or an aromatic ring structure, and (b) ahydrophobic block segment.
 2. The amphiphilic block polymer according toclaim 1, further comprising another hydrophilic block segment.
 3. Theamphiphilic block polymer according to claim 1, wherein four hydrogenatoms attached to the aromatic ring structure represented by D in thegeneral formula (4) are each displaced by fluorine atoms.
 4. Theamphiphilic block polymer according to claim 1, wherein the hydrophobicblock segment has a repeating unit structure represented by the generalformula (8):

wherein: R¹ is selected from the group consisting of a linear, branched,or cyclic alkyl groups of 1 to 18 carbon atoms, -Ph, -Pyr, -Ph-Ph,-Ph-Pyr, —(CH(R⁵)—CH(R⁶)—O)_(p)—R⁷, and —(CH₂)_(m)—(O)_(n)—R⁷, andhydrogen atom(s) in the aromatic ring may be replaced by linear orbranched alkyl group(s) of 1 to 4 carbon atoms, and carbon atom(s) inthe aromatic ring may be replaced by nitrogen atom(s), wherein: prepresents an integer of 1 to 18; m represents an integer of 1 to 36; nrepresents 0 or 1; each of R⁵ and R⁶ represents independently a hydrogenatom or —CH₃; and R⁷ is selected from the group consisting of a hydrogenatom, a linear, branched, or cyclic alkyl group of 1 to 18 carbon atoms,-Ph, -Pyr, -Ph-Ph, -Ph-Pyr, —CHO, —CH₂CHO, —CO—CH═CH₂, —CO—C(CH₃)═CH₂and CH₂COOR₈, and when R⁷ is other than a hydrogen atom, hydrogenatom(s) attached to carbon atom(s) in R⁷ may be replaced by a linear orbranched alkyl group of 1 to 4 carbon atoms, —F, —Cl, or —Br, and carbonatom(s) in the aromatic ring may be replaced by nitrogen atom(s),wherein: R⁸ represents a hydrogen atom or an alkyl group of 1 to 5carbon atoms; Ph represents a phenyl group; and Pyr represents a pyridylgroup.